The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
The reaction of 2,6-dinitroanisole with cyclohexylamine in toluene-dimethyl sulphoxide (DMSO) mixtures was studied at several amine concentrations. In pure toluene and toluene-DMSO mixtures of low DMSO content (≤ 1%) third-order kinetics with respect to the amine are observed. These results are inte...
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| Formato: | Capítulo de libro |
| Lenguaje: | Inglés |
| Publicado: |
1985
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| Acceso en línea: | Registro en Scopus Handle Registro en la Biblioteca Digital |
| Aporte de: | Registro referencial: Solicitar el recurso aquí |
| Sumario: | The reaction of 2,6-dinitroanisole with cyclohexylamine in toluene-dimethyl sulphoxide (DMSO) mixtures was studied at several amine concentrations. In pure toluene and toluene-DMSO mixtures of low DMSO content (≤ 1%) third-order kinetics with respect to the amine are observed. These results are interpreted as a consequence of the aggregation of the nucleophile (dimer) in low-polarity solvents. Association of DMSO with the amine ('mixed dimer') in a solute-solvent hydrogen-bond interaction can be responsible for the observed catalytic effect of DMSO. At higher DMSO contents behaviour typical for amine catalysis was found which is related to considerable additional stabilization of the intermediate complex through solvation by DMSO. |
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| Bibliografía: | Bunnett, J.F., Cartaño, A.V., (1981) J. Am. Chem. Soc., 103, p. 4861 Bunnett, J.F., Randall, R., (1958) J. Am. Chem. Soc., 80, p. 6020 Bernasconi, C.F., (1973) MTP Int. Rev. Sci., Ar. Compds. Org. Chem. Series One, 3, p. 33 Nudelman, N.S., (1980) An. Acad Nac. Ciene. Exactas, Fis. Nal., Buenos Aires, 32, p. 109 Bernasconi, C.F., de Rossi, R.H., Schmid, P., (1977) J. Am. Chem. Soc., 99, p. 4090 Nudelman, N.S., Palleros, D.R., (1981) Acta Sud. Quim., 1, p. 125 Nudelman, N.S., Palleros, D.R., (1983) J. Org. Chem., 48, p. 1607 Nudelman, N.S., Palleros, D.R., (1983) J. Org. Chem., 48, p. 1612 Bamkole, T.O., Hirst, J., Onyido, I., (1982) J. Chem. Soc., Perkin Trans. 2, p. 889 Bernasconi, C.F., Zollinger, H., (1966) Helv. Chim. Acta, 49, p. 2570 Guanti, G., Petrillo, G., Thea, S., (1982) Tetrahedron, 38, p. 505 Brewis, D.M., Chapman, N.B., Paine, J.S., Shorter, J., Wright, D.J., (1974) J. Chem. Soc., Perkin Trans. 2, p. 1787 Consiglio, G., Notto, R., Spinelli, D., (1979) J. Chem. Soc., Perkin Trans. 2, p. 222 Illuminati, G., La Torre, F., Liggieri, G., Sleiter, G., Stegel, F., (1975) J. Am. Chem. Soc., 97, p. 1851 Bernasconi, C.F., Rossi, R., (1976) J. Org. Chem., 41, p. 44 Nudelman, N.S., Palleros, D.R., (1984) J. Chem. Soc., Perkin Trans. 2, p. 1277 Nudelman, N.S., Palleros, D.R., (1981) J. Chem. Soc., Perkin Trans. 2, p. 995 Mancini, P.M.E., Martinez, R.D., Vottero, L.R., Nudelman, N.S., (1984) J. Chem. Soc., Perkin Trans. 2, p. 1133 Reichardt, C., (1979) Angew. Chem., Int. Ed. Engl., 18, p. 98 Bamkole, T.O., Hirst, J., Onyido, I., (1979) J. Chem. Soc., Perkin Trans. 2, p. 1317 Ayediran, D., Bamkole, T.O., Hirst, J., Onyido, I., (1977) J. Chem. Soc., Perkin Trans. 2, p. 1580 Suhr, H., (1965) Justus Liebigs Ann. Chem., 687, p. 175 Suhr, H., (1964) Chem. Ber., 97, p. 3277 Pietra, F., Del Cima, F., (1968) J. Org. Chem., 33, p. 1411 Orvik, J.A., Bunnett, J.F., (1970) J. Am. Chem. Soc., 92, p. 2417 Bunnett, J.F., Sekiguchi, S., Smith, L., (1981) J. Am. Chem. Soc., 103, p. 4865 Terrier, F., (1982) Chem. Rev., 82, p. 77 Bunnett, J.F., Bernasconi, C.F., (1965) J. Am. Chem. Soc., 87, p. 5209 Cox, B., (1973) Annu. Rep. Chem. Soc., Sect. A, p. 249 Parker, A.J., (1969) Chem. Rev., 69, p. 1 Yokoyam, A.T., Taft, R.W., Kamlet, M.J., (1983) Aust. J. Chem., 36, p. 701 Kamlet, M.J., Abboud, J.L., Taft, R.W., (1981) Prog. Phys. Org. Chem., 13, p. 485 Taft, R.W., Gramstad, T., Kamlet, M.J., (1982) J. Chem. Org., 47, p. 4557 Menger, F.M., Smith, J.H., (1969) J. Am. Chem. Soc., 91, p. 4211 Ross, S.D., (1969) Tetrahedron, 25, p. 4427 Bernasconi, C.F., Kaufmann, H., Zollinger, H., (1966) Helv. Chim. Acta, 49, p. 2563 Suhr, H., (1963) Chem. Ber., 67, p. 893 Taft, R.W., (1978) J. Phys. Chem., 82, p. 2477 Madec, C., Laurasan, J., Saumagne, P., (1971) J. Phys. Chem., 75, p. 1157 Reyes, A., Scott, R., (1980) J. Phys. Chem., 84, p. 3600 Kapkan, L.M., Galta, V.F., Titov, E.V., (1980) Ukr. Khim. Zh. (Russ. Ed.), 46, p. 189 Arcoria, A., Maccarone, E., Musumarra, G., Tomaselli, G.A., (1975) Tetrahedron, 31, p. 2523 Kamlet, M.J., Taft, R.W., Carr, P.W., Abraham, M.H., (1982) J. Chem. Soc., Faraday Trans. 1, 78, p. 1689 Busch, M., Gebelein, F., (1927) J. Prakt. Chem., 115, pp. 2, 107 |
| ISSN: | 1472779X |